Azo reactive dyestuffs

ABSTRACT

Dyestuffs of the formula   &lt;IMAGE&gt;   wherein D, R, R1 and R2 have the meaning indicated in the description, and their use for dyeing and printing materials containing hydroxyl groups or amide groups, such as textile fibres, filaments and fabrics of wool, silk or synthetic polyamide or polyurethane fibres, and for dyeing and printing natural or regenerated cellulose with dyeings and prints which are fast to washing.

This is a continuation of application Ser. No. 64,939, filed Aug. 8, 1979 now pending.

The present invention relates to fibre-reactive azo dyestuffs of the formula ##STR2## wherein ##STR3## wherein

R₃ represents halogen, such as fluorine, chlorine or bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or a sulpho, carboxyl, acylamino or 4-sulphophenylazo group,

or wherein ##STR4## wherein

R₄ represents hydrogen, methyl, ethyl or acylamino, or wherein ##STR5## wherein

R₅ represents hydrogen or a sulpho group, and wherein

R=hydrogen or C₁ -C₄ -alkyl and

R₁ and R₂ =hydrogen, optionally substituted alkyl or cycloalkyl or

R₁ and R₂ form a ring with the nitrogen atom, optionally including a further hetero-atom.

The following compounds are examples of amines of the formula

    D--NH.sub.2

on which the dyestuffs are based: 1-amino-2,4-disulpho-benzene, 1-amino-2-sulpho-4-methyl-benzene, 1-amino-2-sulpho-4-ethyl-benzene, 1-amino-2-sulpho-4-methoxy-benzene, 1-amino-2-sulpho-4-ethoxy-benzene, 1-amino-2-sulpho-4-propoxy-benzene, 1-amino-2-sulpho-4-iso-propoxy-benzene, 1-amino-2-sulpho-4-chloro-benzene, 1-amino-2,5-disulpho-benzene, 2-amino-1-sulpho-naphthalene, 2-amino-1,5-disulpho-naphthalene, 2-amino-1,5,7-trisulpho-naphthalene, 2-amino-3,6-disulpho-naphthalene, 2-amino-3,6,8-trisulpho-naphthalene, 1-amino-2-sulpho-4-carboxy-benzene, 1-amino-2-sulpho-4-acetylamino-benzene, 1-amino-2-sulpho-4-(4'-sulphophenylazo)-benzene, 1-amino-2,5-disulpho-4-methyl-benzene and 1-amino-2,5-disulpho-4-acetylamino-benzene.

Examples of suitable optionally substituted alkyl radicals R₁ and R₂ are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, n-hexyl, β-hydroxyethyl, β-methoxyethyl, β-ethoxyethyl, carboxymethyl, β-sulphoethyl, phenylmethyl, β-phenylethyl and cyclohexyl.

Alkyl radicals R₁ and R₂ are preferably C₁ -C₄ -alkyl.

The following radicals are examples of cyclic radicals of the formula ##STR6##

Preferred compounds are those of the formula ##STR7## wherein

R₆ =methyl, chlorine, acetylamino, sulpho, carboxyl, methoxy, ethoxy or 4-sulphophenylazo,

R₇ =hydrogen or methyl,

R₈ =hydrogen or C₁ -C₄ -alkyl and

R₉ =hydrogen or C₁ -C₄ -alkyl,

and those of the formula ##STR8## wherein

R₄ =hydrogen, methyl, ethyl or acetylamino,

R₇ =hydrogen or methyl,

R₈ =hydrogen or C₁ -C₄ -alkyl and

R₉ =hydrogen or C₁ -C₄ -alkyl.

Particularly preferred dyestuffs are those of the formulae (III) and (IV) in which

R₇, R₈ and R₉ represent hydrogen, and those of the formula ##STR9## wherein

R₇ =hydrogen or methyl,

R₈ =hydrogen or C₁ -C₄ -alkyl and

R₉ =hydrogen or C₁ -C₄ -alkyl,

and those of the formula ##STR10## wherein

R₅ has the meaning indicated above,

R₇ =hydrogen or methyl,

R₈ =hydrogen or C₁ -C₄ -alkyl and

R₉ =hydrogen or C₁ -C₄ -alkyl,

and those of the formula ##STR11## wherein

R₅ has the meaning indicated above,

R₇ =hydrogen or methyl,

R₈ =hydrogen or C₁ -C₄ -alkyl and

R₉ =hydrogen or C₁ -C₄ -alkyl.

Particularly preferred compounds are those of the formulae (V) to (VII) in which

R₈ and R₉ =hydrogen.

The invention furthermore relates to a process for the preparation of the compounds of the formula (I). In this process, dyestuffs of the formula ##STR12## wherein

D and R have the meaning indicated above, are subjected to condensation reactions with 2,4,6-trifluoro-1,3,5-triazine, hydrofluoric acid being split off, and the resulting difluoro compounds are reacted with amines of the formula ##STR13## hydrofluoric acid being split off, to give the compounds (I).

The condensation of the dyestuffs (VIII) with s-trifluorotriazine is preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acid, neutral to weakly alkaline pH value.

The condensation reaction is advantageously carried out in the pH range from 3 to 5. The hydrogen fluoride liberated is buffered by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The reaction of the difluoro compound with the amines (IX) is likewise preferably carried out in aqueous solution or suspension, at low temperature and at a neutral to weakly alkaline pH value. The hydrogen fluoride liberated during the reaction is neutralised by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The neutralisation can advantageously also be effected with a second equivalent of amine (IX), in particular with ammonia. Isolation of the difluoro compound is generally omitted.

The dyestuffs (VIII) are obtained by coupling diazotised amines (II) with I-acid under conditions such that coupling is preferably effected in the o-position relative to the hydroxy group of I-acid. However, coupling with a N-acylated I-acid is generally preferred, the acyl radical then being split off by warming the product in an acid or alkaline medium. Possible acyl radicals are, in particular, acetyl, carbamoyl, methoxycarbonyl, ethoxycarbonyl or NH₂ --CO-- (I-acid urea, obtained by reaction with phosgene).

The following compounds are examples of amines (IX): ammonia, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, methylethylamine, ethanolamine, diethanolamine, β-methoxyethylamine, β-ethoxyethylamine, aminoacetic acid, N-methylaminoacetic acid, taurine, N-methyltaurine, benzylamine, β-phenylethylamine, N-methylbenzylamine, pyrrolidine, piperidine and morpholine.

In a further process for the preparation of compounds (I), dyestuffs (VIII) are reacted with the corresponding aminodifluorotriazines, advantageously in an aqueous medium at weakly acid to neutral pH values. It is also possible to first prepare the coupling components of the formula ##STR14## and to couple these with diazotised amines D--NH₂ in a customary manner, to give compounds (I).

The invention furthermore relates to dyestuffs of the formula ##STR15## wherein

R has the meaning indicated above and

R₁₀ and R₁₁ =hydrogen or optionally substituted C₂ -C₄ -alkyl, or

R₁₀ and R₁₁ form a ring with the nitrogen atom, optionally including a further hetero-atom.

The new dyestuffs are suitable for dyeing and printing materials containing hydroxyl groups or amide groups, such as textile fibres, filaments and fabrics of wool, silk or synthetic polyamide or polyurethane fibres and for dyeing and printing natural or regenerated cellulose with dyeings and prints which are fast to washing, the treatment of cellulose materials appropriately being carried out by processes disclosed for reactive dyestuffs, in the presence of acid-binding agents and if necessary by the action of heat.

The formulae indicated for the dyestuffs are those of the corresponding free acids. The dyestuffs were generally isolated, and employed for dyeing, in the form of alkali metal salts, in particular Na salts.

EXAMPLE 1

45.3 g of the dyestuff 2-sulpho-4-methoxy-benzene <1 azo 2> 1-hydroxy-3-sulpho-6-amino-naphthalene are stirred in a mixture of 400 ml of water and 300 g of ice. 13.5 g of 5-trifluorotriazine are added dropwise, during which the hydrofluoric acid liberated is buffered by adding a 20% strength sodium carbonate solution at a rate such that a pH value of 3.5-4.5 is maintained. The mixture is subsequently stirred for some minutes, and complete acylation is confirmed by a diazotisation test.

EXAMPLE 1A

The pH of the clear solution obtained is then adjusted to 9 with 12% strength ammonia solution, and ammonia is subsequently added dropwise at 0°-5° until no further change in pH takes place. In order to separate out the dyestuff, 10% by volume of sodium chloride is added to the clear solution. After filtering off, drying and grinding the product, a red dyestuff powder which is readily soluble in water is obtained. The dyestuff corresponds to the formula ##STR16##

EXAMPLE 1B

The pH of the clear dyestuff solution obtained is adjusted to 9 by adding 9.9 g of cyclohexylamine dropwise. Dilute sodium hydroxide solution is then added so that the pH is kept at 9. The temperature during the 2nd condensation stage is 0°-10°. The condensation reaction has ended when no further sodium hydroxide solution is consumed. The dyestuff is salted out, filtered off and dried. After grinding, a red dyestuff powder which dissolves in water giving a yellowish-tinged red-coloured solution is obtained. The dyestuff corresponds to the formula ##STR17##

The dyestuff used as the starting material is obtained by diazotising 1-amino-2-sulpho-4-methoxy-benzene, coupling the diazotisation product with N-acetyl-I-acid in a weakly acid to neutral pH range, subsequently saponifying the acetyl group with dilute sodium hydroxide solution at 80°-90°, and isolating the product by salting out in a weakly alkaline range.

Dyeing examples Printing instructions

If cotton nettle is printed with a printing paste which contains, per kilogram, 20 g of the dyestuff prepared according to Example 1A, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate/kg of thickener) and 10 g of sodium carbonate and which has been made up to 1 kg with water, and the cotton nettle is dried, steamed at 103° C. for 1 minute, rinsed with hot water and soaped at the boil, a clear, yellowish-tinged red print of good fastness to wet processing and light is obtained.

Padding instructions

30 parts of the dyestuff prepared according to Example 1A are dissolved in 1,000 parts of water. A cotton fabric is padded with this solution and pressed off to a weight increase of 90%. The still moist cotton is treated for 30 minutes at 70° in a bath which contains 300 parts of calcined sodium sulphate and 10 parts of calcined sodium carbonate dissolved in 1,000 parts of water. The dyeing is then finished in the customary manner. A brilliant scarlet dyeing with outstanding fastness to wet processing and light is obtained.

Dyeing instructions

168 ml of water of 20°-25° are initially introduced into a dyeing beaker which has a capacity of 300 ml and is in a waterbath which can be heated. 0.3 g of the dyestuff obtained according to Example 1A is mixed thoroughly with 2 ml of cold water to form a paste, and 30 ml of hot water (70°) are added; the dyestuff thereby dissolves. The dyestuff solution is added to the initially introduced water and 10 g of cotton yarn are kept continuously in motion in this dye liquor. The temperature of the dye liquor is increased to 40°-50° in the course of 10 minutes, 10 g of anhydrous sodium sulphate are added and dyeing is continued for 30 minutes. 4 g of anhydrous sodium carbonate are then added to the dye liquor and dyeing is carried out at 40°-50° for 60 minutes. The dyed material is then taken out of the dye liquor, the adhering liquor is removed by wringing out or pressing off and the material is rinsed first with cold water and then with hot water, until the rinsing liquor is no longer stained. The dyed material is then soaped at the boiling point for 20 minutes in 200 ml of a liquor which contains 0.2 g of a sodium alkyl-sulphate, rinsed again and dried at 60°-70° in a drying cabinet. A brilliant scarlet dyeing of good fastness to washing and light is obtained.

If the procedure followed is according to the statements of Example 1, but instead of the aminoazo dyestuff used in that example, compounds which are obtainable by diazotising the diazo components listed in column 1, coupling the diazotisation products with the acetyl compounds of the coupling components given in column 2 and saponifying the acetyl group are employed, and instead of ammonia or cyclohexylamine, one of the amines described in column 3 is used, according to variant A or B, equally valuable dyestuffs which dye cotton, by one of the dyeing processes mentioned, in one of the shades listed in column 4 result.

    __________________________________________________________________________     Example                                                                             Column 1  Column 2  Column 3   Variant                                                                             Column 4                              __________________________________________________________________________     2    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    scarlet                                    4-methoxy-benzene                                                                        6-amino-napthalene                                              3    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethylamine A    "                                          4-methoxy-benzene                                                                        6-amino-naphthalene                                             4    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    "                                          4-methoxy-benzene                                                                        6-amino-naphthalene                                             5    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              A    "                                          4-methoxy-benzene                                                                        6-amino-naphthalene                                             6    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    "                                          4-methoxy-benzene                                                                        6-amino-naphthalene                                             7    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      n-butylamine                                                                              B    "                                          4-methoxy-benzene                                                                        6-amino-naphthalene                                             8    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                9    1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                10   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethylamine A    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                11   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                12   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                13   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                14   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      n-butylamine                                                                              B    yellowish-tinged                           benzene   6-amino-naphthalene       orange                                15   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      ammonia    A    scarlet                                    ethoxy-benzene                                                                           6-amino-naphthalene                                             16   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    "                                          ethoxy-benzene                                                                           6-amino-naphthalene                                             17   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      ethylamine B    "                                          ethoxy-benzene                                                                           6-amino-naphthalene                                             18   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      ammonia    A    yellowish-tinged                           chloro-benzene                                                                           6-amino-naphthalene       orange                                19   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    yellowish-tinged                           chloro-benzene                                                                           6-amino-naphthalene       orange                                20   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              A    yellowish-tinged                           chloro-benzene                                                                           6-amino-naphthalene       orange                                21   1-amino-2-sulpho-4-                                                                      1-hydroxy-3-sulpho-                                                                      diethylamine                                                                              B    yellowish-tinged                           chloro-benzene                                                                           6-amino-naphthalene       orange                                22   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                23   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                24   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      aminoacetic acid                                                                          B    redish-tinged                              4-methyl-benzene                                                                         6-amino-naphthalene       orange                                25   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      taurine    B    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                26   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      N--methyltaurine                                                                          B    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                27   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                28   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    reddish-tinged                             4-methyl-benzene                                                                         6-amino-naphthalene       orange                                29   1-amino-2,4-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia    A    yellowish-tinged                           sulpho-benzene                                                                           6-amino-naphthalene       orange                                30   1-amino-2,4-di-                                                                          1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    yellowish-tinged                           sulpho-benzene                                                                           6-amino-naphthalene       orange                                31   1-amino-2,4-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethylamine B    yellowish-tinged                           sulpho-benzene                                                                           6-amino-naphthalene       orange                                32   1-amino-2,4-di-                                                                          1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    yellowish-tinged                           sulpho-benzene                                                                           6-amino-naphthalene       orange                                33   1-amino-2,4-di-                                                                          1-hydroxy-3-sulpho-                                                                      n-butylamine                                                                              B    yellowish-tinged                           sulpho-benzene                                                                           6-amino-naphthalene       orange                                34   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      ammonia    A    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                35   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                36   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      ethylamine B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                37   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                38   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      n-butylamine                                                                              B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                39   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      n-hexylamine                                                                              B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                40   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      morpholine B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                41   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                42   1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      benzylamine                                                                               B    yellowish-tinged                           pho-benzene                                                                              6-amino-naphthalene       orange                                43   1-amino-2,5-                                                                             1-hydroxy-3-sulpho-                                                                      β-phenylethylamine                                                                   B    yellowish-tinged                           disulpho-benzene                                                                         6-amino-naphthalene       orange                                44   1-amino-2,5-                                                                             1-hydroxy-3-sulpho-                                                                      N--methyl-benzylamine                                                                     B    yellowish-tinged                           disulpho-benzene                                                                         6-amino-naphthalene       orange                                45   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    deeply reddish-                            naphthalene                                                                              6-methylamino-            tinged orange                                        naphthalene                                                     46   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    deeply reddish-                            naphthalene                                                                              6-methylamino-            tinged orange                                        naphthalene                                                     47   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              A    deeply reddish-                            naphthalene                                                                              6-methylamino-            tinged orange                                        naphthalene                                                     48   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    deeply reddish-                            naphthalene                                                                              6-methylamino-            tinged orange                                        naphthalene                                                     49   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      morpholine B    deeply reddish                             naphthalene                                                                              6-methylamino-            tinge orange                                         naphthalene                                                     50   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    deeply reddish                             naphthalene                                                                              6-methylamino-            tinged orange                                        naphthalene                                                     51   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         52   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         53   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      aminoacetic acid                                                                          B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         54   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      taurine    B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         55   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      N--methylamine                                                                            B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         56   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         57   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         58   2-amino-1-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      β-methoxyethylamine                                                                  B    deeply reddish-                            naphthalene                                                                              6-amino-naphthalene       tinged orange                         59   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia    A    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     60   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     61   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethylamine A    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     62   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              A    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     63   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     64   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      morpholine B    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     65   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      n-propylamine                                                                             B    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     66   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    reddish-tinged                             sulpho-naphthalene                                                                       6-methylamino-            orange                                               naphthalene                                                     67   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia    A    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                68   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                69   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethylamine A    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                70   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    reddish-tinged                             sulpho-naphthaline                                                                       6-amino-naphthalene       orange                                71   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                72   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      βmethoxyethylamine                                                                   B    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                73   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      morpholine B    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                74   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      n-propylamine                                                                             B    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                75   2-amino-1,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      isp-propylamine                                                                           B    reddish-tinged                             sulpho-naphthalene                                                                       6-amino-naphthalene       orange                                76   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      ammonia    A    orange                                     sulpho-naphthalene                                                                       6-amino-naphthalene                                             77   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             78   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      ethylamine B    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             79   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             80   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             81   2-amino-1,5,7-tri-                                                                       1-hydroxy-3-sulpho-                                                                      benzylamine                                                                               B    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             82   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia    A    scarlet                                    sulpho-naphthalene                                                                       6-amino-naphthalene                                             83   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             84   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             85   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              A    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             86   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    "                                          sulpho-naphthalene                                                                       d-amino-naphthalene                                             87   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethylamine A    "                                          sulpho-naphthalene                                                                       6-amino-naphthalene                                             88   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia    A    "                                          sulpho-naphthalene                                                                       6-methylamino-                                                                 naphthalene                                                     89   2-amino-3,6-di-                                                                          1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    "                                          sulpho-naphthalene                                                                       6-methylamino-                                                                 naphthalene                                                     90   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      ammonia    A    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               91   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               92   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               93   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      ethylamine A    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               94   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      diethylamine                                                                              B    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               95   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               96   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               97   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               98   2-amino-3,6,8-                                                                           1-hydroxy-3-sulpho-                                                                      n-propylamine                                                                             B    "                                          trisulpho-                                                                               6-amino-naphthalene                                                  naphthalene                                                               99   1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   100  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   101  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethylamine A    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   102  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   103  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      diethanolamine                                                                            B    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   104  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      cyclohexylamine                                                                           B    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   105  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      morpholine B    bluish-tinged                              4-acetylamino-                                                                           6-amino-naphthalene       scarlet                                    benzene                                                                   106  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ammonia    A    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              107  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      methylamine                                                                               A    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              108  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethylamine A    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              109  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      dimethylamine                                                                             A    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              110  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      diethylamine                                                                              B    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)benzene                                                               111  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      ethanolamine                                                                              B    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        aze)-benzene                                                              112  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      morpholine B    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              113  1-amino-2-sulpho-                                                                        1-hydroxy-3-sulpho-                                                                      iso-propylamine                                                                           B    yellowish-tinged                           4-(4'-sulphophenyl-                                                                      6-amino-naphthalene       red                                        azo)-benzene                                                              114  1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      ammonia    A    orange                                     pho-4-methylbenzene                                                                      6-amino-naphthalene                                             115  1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      methylamine     "                                          pho-4-methylbenzene                                                                      6-amino-naphthalene                                             116  1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      dimethylamine   "                                          pho-4-methylbenzene                                                                      6-amino-naphthalene                                             117  1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      ethylamine      "                                          pho-4-methylbenzene                                                                      6-amino-naphthalene                                             118  1-amino-2,5-disul-                                                                       1-hydroxy-3-sulpho-                                                                      iso-propylamine "                                          pho-4-methylbenzene                                                                      6-amino-naphthalene                                             119  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      cyclohexylamine orange                                     sulpho-4-methyl-                                                                         6-amino-naphthalene                                                  benzene                                                                   120  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethanolamine    "                                          sulpho-4-methyl-                                                                         6-amino-naphthalene                                                  benzene                                                                   121  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ammonia         scarlet                                    sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              122  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      methylamine     "                                          sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              123  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      ethylamine      "                                          sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              124  1-amino-2,5-di                                                                           1-hydroxy-3-sulpho-                                                                      ethanolamine    "                                          sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              125  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      cyclohexylamine "                                          sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              126  1-amino-2,5-di-                                                                          1-hydroxy-3-sulpho-                                                                      iso-propylamine "                                          sulpho-4-acetyl-                                                                         6-amino-naphthalene                                                  aminobenzene                                                              __________________________________________________________________________

EXAMPLE 127

50.3 g of the azo dyestuff 2,5-disulpho-benzene <1 azo 2> 1-hydroxy-3-sulpho-6-amino-naphthalene are dissolved in a mixture of 250 ml of water and 150 g of ice. 13.5 g of 5-trifluorotriazine are then added dropwise, and during this addition the pH value is kept between 3.5 and 4.5 by simultaneously adding 20% strength sodium carbonate solution. When the condensation reaction has ended, the mixture is further stirred for some minutes. 13.6 g of cyclohexylamine hydrochloride are added and the pH value is then adjusted to 9 with dilute sodium hydroxide solution. The mixture is stirred at pH 8.5-9 until no further sodium hydroxide solution is consumed. The temperature during the second condensation reaction is between 2 and 10°. The dyestuff is salted out, filtered off, dried and ground. It is identical to the product obtained according to Example 35. 

We claim:
 1. Dyestuffs of the formula ##STR18## wherein ##STR19## wherein R₃ represents halogen selected from the group consisting of fluorine, chlorine and bromine; C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or a sulpho, carboxyl, acylamino or 4-sulphophenylazo group,or wherein ##STR20## wherein R₄ represents hydrogen, methyl, ethyl or acylamino, or wherein ##STR21## wherein R₅ represents hydrogen or a sulpho group, and wherein R=hydrogen or C₁ -C₄ -alkyl and R₁ and R₂ =hydrogen, unsubstituted or substituted alkyl or cycloalkyl or R₁ and R₂ form a ring with the nitrogen atom including a further hetero-atom.
 2. Dyestuffs of the formula ##STR22## wherein R₆ =methyl, chlorine, acetylamino, sulpho, carboxyl, methoxy, ethoxy or 4-sulphophenylazo,R₇ =hydrogen or methyl, R₈ =hydrogen or C₁ -C₄ -alkyl and R₉ =hydrogen or C₁ -C₄ -alkyl.
 3. Dyestuffs of the formula ##STR23## wherein R₇, R₈ and R₉ have the meaning indicated in claim 2 andR₄ =hydrogen, methyl, ethyl or acetylamino.
 4. Dyestuffs of the formula ##STR24## wherein R₇, R₈ and R₉ have the meaning indicated in claim
 2. 5. Dyestuff of the formula ##STR25## wherein R₅ has the meaning indicated in claim 1 andR₇ =hydrogen or methyl, R₈ =hydrogen or C₁ -C₄ -alkyl and R₉ =hydrogen or C₁ -C₄ -alkyl.
 6. Dyestuff of the formula ##STR26## wherein R₅ has the meaning indicated in claim 1 andR₇ =hydrogen or methyl, R₈ =hydrogen or C₁ -C₄ -alkyl and R₉ =hydrogen or C₁ -C₄ -alkyl.
 7. Dyestuffs of the formula ##STR27## wherein R has the meaning indicated in claim 1 andR₁₀ and R₁₁ =hydrogen, or unsubstituted or substituted C₂ -C₄ -alkyl, or R₁₀ and R₁₁ form a ring with the nitrogen atom or R₁₀ and R₁₁ form a ring with the nitrogen atom and a further hetero-atom.
 8. Dyestuffs of claim 1,in which R₁ and R₂ =H, C₁ -C₄ -alkyl or C₂ -C₄ -hydroxyalkyl. 